The Transfer Dehydrogenation Method Enables a Family of High Crystalline Benzimidazole‐linked Cu (II)‐phthalocyanine‐based Covalent Organic Frameworks Films

Abstract Heterocycle‐linked phthalocyanine‐based COFs with close‐packed π–π conjugated structures are a kind of material with intrinsic electrical conductivity, and they are considered to be candidates for photoelectrical devices. Previous studies have revealed their applications for energy storage, gas sensors, and field‐effect transistors. However, their potential application in photodetector is still not fully studied. The main difficulty is preparing high‐quality films. In our study, we found that our newly designed benzimidazole‐linked Cu (II)‐phthalocyanine‐based COFs (BICuPc‐COFs) film can hardly formed with a regular aerobic oxidation method. Therefore, we developed a transfer dehydrogenation method with N‐benzylideneaniline (BA) as a mild reagent. With this in hand, we successfully prepared a family of high crystalline BICuPc‐COFs powders and films. Furthermore, both of these new BICuPc‐COFs films showed high electrical conductivity (0.022–0.218 S/m), higher than most of the reported COFs materials. Due to the broad absorption and high conductivity of BICuPc‐COFs, synaptic devices with small source‐drain voltage (V DS =1 V) were fabricated with response light from visible to near‐infrared. Based on these findings, we expect this study will provide a new perspective for the application of conducting heterocycle‐linked COFs in synaptic devices.